JP7068895B2 - Dishwasher detergent composition - Google Patents

Description

The present invention relates to a dishwasher detergent composition.

In recent years, dishwashers for washing tableware, cooking utensils, etc. (objects to be washed) have become widespread not only in kitchens such as hotels, restaurants, and food service centers, but also in ordinary households. For washing with a dishwasher, a special detergent (dishwasher detergent) is generally used.
When the object to be washed is washed in the dishwasher, it is dried in the dishwasher.

For example, Patent Document 1 proposes a detergent composition containing an amine compound, an alkaline compound, and water.

Japanese Unexamined Patent Publication No. 2016-183242

However, with the liquid detergent of Patent Document 1, water droplets tend to remain on the object to be cleaned after drying.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dishwasher detergent composition having good traces of water droplets.

The dishwasher detergent composition of the present invention includes the following aspects.
[1] Containing component (A) and component (B),
The component (A) is a surfactant, and the component (A) is a surfactant.
The component (B) is a compound represented by the following formula (b-1).
The component (A) contains a non-soap-based anionic surfactant (a1).
A dishwasher detergent composition having a mass ratio of the component (a1) / the component (B) of 0.1 to 500.
R ¹ -N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
(In the formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group of a branched chain of the number 8-18; n is an integer of 2-6.)
[2] Further containing a chelating agent (C),
The dishwasher detergent composition according to [1], wherein the chelating agent has a molecular weight of 800 or less.
[3] The detergent composition for a dishwasher according to [1] or [2], wherein the content of the component (a1) is 40% by mass or more with respect to the total mass of the component (A).
[4] The dishwasher detergent composition according to any one of [1] to [3], wherein the component (A) contains a nonionic surfactant (a2).
[5] The detergent composition for a dishwasher according to any one of [1] to [4], further comprising an acrylic acid-based water-soluble polymer (D).

The detergent composition for a dishwasher of the present invention is excellent in the effect of suppressing the residue of water droplets.

≪Dishwasher detergent composition≫
The dishwasher detergent composition of the present invention contains the component (A) and the component (B).
The detergent composition for a dishwasher of the present invention may be a liquid or a powder.

<Ingredient (A)>
The component (A) is a surfactant containing a non-soap-based anionic surfactant (a1) (hereinafter, also referred to as “component (a1)”).
In addition to the component (a1), the component (A) includes a nonionic surfactant (a2) (hereinafter, also referred to as "component (a2)"), a quaternary ammonium salt-type surfactant, an amphoteric surfactant, and an amine. It may contain at least one surfactant (a3) (hereinafter, also referred to as “(a3) component”) selected from the group consisting of an oxide-type surfactant and an amine-type surfactant.

The component (a1) is a non-soap-based anionic surfactant. The "non-soap-based anionic surfactant" means an anionic surfactant excluding saturated or unsaturated fatty acid salts (soap) having 8 to 24 carbon atoms.
The component (a1) is roughly classified into a sulfonate type, a sulfate ester type, a carboxylate type, and a phosphate ester type.
Examples of the sulfonate type include alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, alkyl sulfosuccinate, and dialkyl sulfosuccinic acid. And so on.
Examples of the sulfate ester salt type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, and polyoxyalkylene alkenyl ether sulfate ester salts.
Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid-based anionic surfactants and the like.
The anionic surfactant preferably has an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 18 carbon atoms is preferable. The alkyl group or the alkenyl group may be linear or branched.
Among them, the sulfonate type is preferable because the effect of suppressing the residual water droplets is good, and the alkane sulfonate and the dialkyl sulfosuccinate are particularly preferable.
Examples of the salt constituting the anionic surfactant include metal salts such as sodium, potassium, magnesium and calcium.
Specific examples of the alkane sulfonate include sodium tetradecane sulfonate, sodium hexadecane sulfonate, sodium octadecane sulfonate and the like.
Among these, a mixture of secondary sodium alkanesulfonate having 14 or more carbon atoms and 17 or less carbon atoms is preferable.
Examples of commercially available products include HOSTAPUR SAS30 manufactured by Clariant Japan, MERSOLATE H-95 manufactured by Bayer Corporation, and Ramtel PS manufactured by Kao Corporation.

The component (a2) is a nonionic surfactant. As the component (a2), a polyoxyalkylene type nonionic surfactant, an alkylpolyglycoside type nonionic surfactant, an aliphatic alkanolamide type nonionic surfactant, a sorbitan fatty acid ester type nonionic surfactant, and an alkylmonoglyceryl ether type nonionic. Examples thereof include a surfactant, a fatty acid monoglyceride type nonionic surfactant, and a sucrose fatty acid ester type nonionic surfactant.

As the polyoxyalkylene type nonionic surfactant, a compound represented by the following formula (a2-1) (hereinafter, also referred to as “compound (a2-1)”) is preferable.
R ²¹ -X-[(EO) _s / (PO) _t ] -R ²² ... (a2-1)

In the formula (a2-1), R ²¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, and R ²² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number of carbon atoms. It is an alkenyl group of 2 to 6, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average number of repetitions of EO, a number of 1 to 20, and t represents an average number of repetitions of PO. Is a number from 1 to 20.

In the formula (a2-1), the hydrocarbon group of R ²¹ has 6 to 22 carbon atoms, preferably 8 to 22 and more preferably 10 to 18. The hydrocarbon group of R ²¹ may be a straight chain or a branched chain, and may or may not have an unsaturated bond.
Examples of -X- include -O-, -COO-, -CONH- and the like.
The number of carbon atoms of the alkyl group in R ²² is 1 to 6, preferably 1 to 3.
The alkenyl group in R ²² has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.

The compound (a2-1) in which -X- is -O-, -COO- or -CONH- is a primary or secondary higher alcohol (R ²¹ -OH) or higher fatty acid (R ²¹ -COOH). Alternatively, it can be obtained from a higher fatty acid amide (R ²¹ -CONH) as a raw material. R ²¹ in these raw materials is the same as R ²¹ in the formula (a2-1).

s is a number of 1 to 20, preferably 3 to 10.
t is a number of 1 to 10, preferably 2 to 8.

When t is 1 or more, that is, when the compound (a2-1) has EO and PO, the method for adding ethylene oxide and propylene oxide is not particularly limited, and for example, a random addition method or a block addition method may be used. Examples of the block addition method include a method of adding ethylene oxide and then adding propylene oxide, a method of adding propylene oxide and then adding ethylene oxide, and a method of adding ethylene oxide and then adding propylene oxide, and further adding ethylene oxide. How to do it.

As the compound (a2-1), in particular, -X- is -O- (alcohol-type nonionic surfactant) or -X- is -COO- and R ²² has 1 to 6 carbon atoms. A compound (fatty acid alkyl (alkenyl) ester) which is an alkyl group or an alkenyl group having 2 to 6 carbon atoms is preferable.

When —X— is —O—, the carbon number of R ²¹ is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18. When —X— is —O—, R ²² is preferably a hydrogen atom.

When -X- is -COO-, the carbon number of R ²¹ is preferably 9 to 21, and more preferably 11 to 21. When -X- is -COO-, R ²² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
Specifically, NNAEP manufactured by Lion Specialty Chemicals, Sannonic series manufactured by Sanyo Chemicals, Narrow Acty series, Neugen series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Purafac manufactured by BASF, Lutensol series, and ADEKA. Pluronic series, Kao's Emargen series, etc.

As the alkylpolyglycoside type nonionic surfactant, a nonionic surfactant represented by the following formula (a2-2) is preferable.
R ²⁵ (OR ²⁶ ) _x Gy ... ( _a2-2 )
In the formula (a2-2), R ²⁵ represents an alkyl group, an alkenyl group or an alkylphenyl group, preferably an alkyl group having 8 or more and 18 or less carbon atoms, preferably 12 or more and 14 or less carbon atoms in a linear or branched chain, and R ²⁶ indicates an alkylene group having 2 or more and 4 or less carbon atoms, and Gy indicates a residue derived from a reduced sugar having 5 or 6 carbon atoms. x indicates the average number of added moles, which is a number of 0 or more and 5 or less. y indicates a number whose average value is 1 or more and 5 or less.
In the formula (a2-2), R ²⁵ is a linear or branched alkyl group having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less, preferably 14 or less carbon atoms from the viewpoint of storage stability.
In the formula (a2-2), x is preferably 0 or more and 2 or less, and more preferably 0, from the viewpoint of storage stability. From the viewpoint of storage stability, y is preferably 1.1 or more, preferably 1.5 or less, and more preferably 1.4 or less. In addition, y is a measured value by the proton NMR method.
In formula (a2-2), G includes residues derived from one or more monosaccharides selected from glucose and fructose in terms of their availability and cost. Further, G includes residues derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from the monosaccharide of glucose.

As the aliphatic alkanolamide type nonionic surfactant, a nonionic surfactant selected from the group consisting of fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide and having an HLB of 9.5 or more and less than 12 is preferable.
In the present invention, the "fatty acid alkanolamide" is produced by, for example, a reaction between a fatty acid, a fatty acid alkyl ester, a fatty acid chloride, an oil or fat, and an alkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, etc.). That is, the fatty acid monoalkanolamide and / or the fatty acid dialkanolamide.
The "polyoxyethylene fatty acid alkanolamide" refers to a fatty acid alkanolamide in which an oxyethylene group is introduced.
In the present invention, "HLB" is represented by IOB × 10 in the organic conceptual diagram.
The IOB in the organic conceptual diagram means the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, "inorganic value (IV) / organic value (OV)".
The organic conceptual diagram was proposed by Akira Fujita, and the details thereof are described in "Pharmaceutical Bulletin", 1954, vol. 2,2, pp. 163-173; "The Domain of Chemistry", 1957, vol. 11,10, pp. 719-725; "Fragrance Journal", 1981, vol. 50, pp. It is explained in 79-82 and the like. That is, the source of all organic compounds is methane (CH ₄ ), and all other compounds are regarded as derivatives of methane, and constant values are set for their carbon number, substituent, transformation part, ring, etc. Scores are added to obtain organic and inorganic values. Then, these values are plotted on a diagram with the organic value as the X-axis and the inorganic value as the Y-axis. This organic conceptual diagram is also shown in "Organic Conceptual Diagram-Basics and Applications-" (Yoshio Koda, Sankyo Publishing, 1984) and the like.

The component (a3) is at least one surfactant selected from the group consisting of a quaternary ammonium salt type surfactant, an amphoteric surfactant, an amine oxide type surfactant, and an amine type surfactant. ..

[Quaternary ammonium salt type surfactant]
Examples of the quaternary ammonium salt type surfactant include tetra short chain (alkyl having 1 to 4 carbon atoms) ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, and tetrabutylammonium salt; octyltrimethylammonium. Salt, decyltrimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, lauryltrimethylammonium salt, cetyltrimethylammonium salt, palmityltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt , Dodecyldimethylethylammonium salt, tetradecyldimethylethylammonium salt, lauryldimethylethylammonium salt, cetyldimethylethylammonium salt, stearyldimethylethylammonium salt, octyldiethylmethylammonium salt, decyldiethylmethylammonium salt, dodecyldiethylmethylammonium salt, Long-chain (alkyl with 8 to 18 carbon atoms) tri-short chain (alkyl with 1 or 2 carbon atoms) ammonium salt such as tetradecyldiethylmethylammonium salt, cetyldiethylmethylammonium salt, stearyldiethylmethylammonium salt; dioctyldimethylammonium salt , Didecyldimethylammonium salt, Didodecyldimethylammonium salt, Ditetradecyldimethylammonium salt, Disetyldimethylammonium salt, Distearyldimethylammonium salt, Dioctylmethylethylammonium salt, Didecylmethylethylammonium salt, Didodecylmethylethylammonium Dilong chain (alkyl with 8 to 18 carbon atoms) dishort chain (alkyl with 1 or 2 carbon atoms) ammonium such as salt, ditetradecylmethylethylammonium salt, disetylmethylethylammonium salt, distearylmethylethylammonium salt, etc. Salt; Long chain (alkyl with 8 to 18 carbon atoms) dishort chain (alkyl with 1 or 2 carbon atoms) hydroxyalkyl (1 or 2 carbon atoms) ammonium salt such as stearyldimethylhydroxyethylammonium; [3 (trimethoxysilyl) )] Dishort chain (alkyl with 1 or 2 carbon atoms) long chain (alkyl with 8 to 18 carbon atoms) ammonium salt having a trialkoxysilylalkyl group (4 to 10 carbon atoms) such as propyl (dimethyl) octadecylammonium salt. Ammonium nitrate; Benzyltrimethylammonium salt; benzalkonium salt; benzethonium salt can be mentioned. Among these, long-chain (alkyl with 8 to 18 carbon atoms) tri-short chain (alkyl with 1 or 2 carbon atoms) ammonium salt, di-long chain (alkyl with 8 to 18 carbon atoms) di-short chain (alkyl with 1 or 2 carbon atoms) Alkyl) ammonium salt, benzyltrimethylammonium salt, benzalconium salt, benzethonium salt and the like are preferable, long-chain (alkyl having 8 to 18 carbon atoms) tri-short chain (alkyl having 1 or 2 carbon atoms) ammonium salt, di-length. A chain (alkyl having 8 to 12 carbon atoms) di short chain (alkyl having 1 or 2 carbon atoms) ammonium salt is more preferable.

Examples of the salt include halides such as chlorine, bromine and iodine; hydroxides; sulfonic acid esters having 1 to 5 carbon atoms, sulfuric acid esters, nitrate esters and the like.

[Amphoteric surfactant]
As the amphoteric surfactant, a compound represented by the following formula (a3-2) is preferable.
R ^12- (A) _p -N ⁺ (-R ¹³ ) (-R ¹⁴ ) -R ¹⁵ -R ¹⁶ ... (a3-2)
In formula (a3-2), R ¹² is a linear or branched alkyl group having 8 to 18 carbon atoms; R ¹³ and R ¹⁴ are independently alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms, respectively. A is -C = O (-NH-X)-; X is an alkylene group having 1 to 4 carbon atoms; p is a number of 0 or 1; R ¹⁵ is 1 to 2 carbon atoms. Is an alkylene group of ^; R ¹⁶ is -CO _2- ^or -SO _3- .
For example, octanoic acid amide propyl dimethylaminoacetic acid betaine, decanoic acid amide propyl dimethylaminoacetic acid betaine, lauric acid amide propyl dimethylamino acetate betaine, myristic acid amide propyl dimethylamino acetate betaine, stearate amide propyl dimethylamino acetate betaine, oleic acid amide. Propyldimethylaminoacetic acid betaine, coconut oil fatty acid amide propyldimethylaminoacetic acid betaine, palm oil fatty acid amide propyldimethylaminoacetic acid betaine, palm kernel oil fatty acid amide propyldimethylaminoacetic acid betaine, octyldimethylaminoacetic acid betaine, decyldimethylaminoacetic acid betaine, lauryl Dimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, oleyldimethylaminoacetic acid betaine, octanoic acid amide propyl hydroxysulfobetaine, decanoic acid amide propyl hydroxysulfobetaine, lauric acid amide propyl hydroxysulfobetaine, myristic acid amide Propyl hydroxysulfobetaine, stearate amide propyl hydroxysulfobetaine, oleate amide propyl hydroxysulfobetaine, coconut oil fatty acid amide propyl hydroxysulfobetaine, palm oil fatty acid amide propyl hydroxysulfobetaine, palm kernel oil fatty acid amide propyl hydroxysulfobetaine, octyl Examples thereof include hydroxysulfobetaine, decylhydroxysulfobetaine, lauryl hydroxysulfobetaine, myristyl hydroxysulfobetaine, stearyl hydroxysulfobetaine, and oleyl hydroxysulfobetaine.

[Amine oxide type surfactant]
As the amine oxide type surfactant, a compound represented by the following formula (a3-3) is preferable.

In the formula (a3-3), R ¹⁷ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group having a branched chain of 8 to ¹⁸ ; R ¹⁹ and R ²⁰ are independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; Is an alkylene group having 1 to 4 carbon atoms; B is -CONH-, -NHCO-, -COO-, -OCO- or -O-; r is a number of 0 or 1; ^Z- is a pair. It is an ion.
For example, alkyldimethylamine oxides such as lauryldimethylamine oxides, coconut alkyldimethylamine oxides and n-dodecyldimethylamine oxides; alkyldiethylamine oxides such as lauryldiethylamine oxides; alkanoylamide alkyldimethylamine oxides such as lauric acidamidepropyldimethylamine oxides. And so on.

[Amine-type surfactant]
The amine-type surfactant is a primary amine, a secondary amine, or a tertiary amine that functions as a surfactant (however, excluding those corresponding to the component (B)). As the amine-type surfactant, an amine compound represented by the following formula (a3-4) is preferable.
R ² R ³ R ⁴ N ... (a3-4)
In formula (a3-4), R ² , R ³ and R ⁴ are substituents on N, R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 8 to 21 carbon atoms or an alkenyl. A group or a hydroxyalkyl group having 1 to 4 carbon atoms; R ³ is a hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or an aminoalkyl group having 1 to 4 carbon atoms. Yes; R ⁴ is an alkyl or alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or a group represented by R ⁵ -X- (CH ₂ ) _m- ; R ⁵ is. A linear alkyl or alkenyl group having 8 to 21 carbon atoms, an alkyl or alkenyl group having a branched chain having 8 to 21 carbon atoms; X is -O-, -C (O) NR ^6- , or -NH. -, R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms; m is an integer of 1 to 5 carbon atoms.
The compound of the formula (a3-4) preferably contains at least one alkyl group or alkenyl group having 8 to 21 carbon atoms, preferably 1 to 2 carbon atoms.

Among them, the compound represented by the following formula (a3-5) is preferable.

In the formula (a3-5), R ⁷ is a linear alkyl group having 13 to 21 carbon atoms, an alkyl group having a branched chain having 13 to 21 carbon atoms, a linear alkenyl group having 13 to 21 carbon atoms, or a carbon number of carbon atoms. It is an alkenyl group of a branched chain of 13 to 21; R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms; R ⁹ is an alkyl group having 1 to 4 carbon atoms. R ¹⁰ and R ¹¹ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

In the formula (a3-5), R ⁷ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms. The number of carbon atoms of the alkyl group and the alkenyl group in ^R7 is 13 to 21, respectively, and the foam-suppressing effect is further enhanced, so that the carbon number is preferably 15 to 21, and more preferably 15 to 19.
The number of hydroxy groups ⁱⁿ the hydroxyalkyl group in R8 may be one or two or more. Among them, as R8, a hydrogen atom and an alkyl group having 1 to ⁴ carbon atoms are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
The number of carbon atoms of the alkylene group in R9 is ¹ to 4, preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3. The number of carbon atoms of the alkyl groups in R ¹⁰ and R ¹¹ is 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. Among them, R ¹⁰ and R ¹¹ are preferably alkyl groups having 1 to 4 carbon atoms, respectively, and are preferably the same as each other.
Specific examples of the compound represented by the formula (a3-5) include myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearate dimethylaminopropylamide, and behen because the foam-suppressing effect is more easily obtained. Acid dimethylaminopropylamide is preferable, palmitate dimethylaminopropylamide, stearate dimethylaminopropylamide and behenic acid dimethylaminopropylamide are more preferable, and palmitate dimethylaminopropylamide and stearate dimethylaminopropylamide are particularly preferable.

Examples of the amine-type surfactant other than the compound represented by the formula (a3-5) include coconut alkylamine, beef alkylamine, oleylamine, octylamine, dodecylamine, octadecylamine, di-cured beef alkylamine, and coconut alkyl. Didimethylamine, Beef Alkyldimethylamine, Dodecyldimethylamine, Hexadecyldimethylamine, Octadecyldimethylamine, Behenyldimethylamine, Dioleylmethylamine, Didecylmethylamine, N-Palm Alkyl-1,3-Diaminopropane, N-Beef Alkyl- Examples thereof include 1,3-diaminopropane, N-hardened beef fat alkyl-1,3-diaminopropane, and 3,3'-diamino-N-methyldipropylamine.

The component (A) may be used alone or in combination of two or more.
The content of the component (A) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass with respect to the total mass of the dishwasher detergent composition. % Is more preferable.
When the content of the component (A) is within the above range, it is easy to improve the effect of suppressing the residue of water droplets, and it is easy to improve the detergency and the suppression of foaming.

The content of the component (a1) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.1 to 1% by mass with respect to the total mass of the dishwasher detergent composition. % Is more preferable.
When the content of the component (a1) is within the above range, it becomes easy to improve the effect of suppressing the residual water droplets.

The content of the component (a1) is preferably 40% by mass or more, more preferably 60 to 100% by mass, based on the total mass of the component (A).
When the content of the component (a1) is within the above range, it becomes easier to improve the effect of suppressing the residual water droplets.

The content of the component (a2) is preferably 0 to 50% by mass, more preferably 10 to 40% by mass, based on the total mass of the component (A).
When the content of the component (a2) is within the above range, it becomes easy to improve the effect of suppressing the residual water droplets.

<Ingredient (B)>
The component (B) is a compound represented by the following formula (b-1).
R ¹ -N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
In formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or a carbon number of carbon atoms. It is an alkenyl group of 8-18 branched chains; n is an integer of 2-6.

Examples of the component (B) include N- (3-aminopropyl) -N-decylpropane-1,3-diamine, N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine, and N. -(3-Aminoethyl) -N-dodecylpropane-1,3-diamine, N- (3-aminopropyl) -N-tetradecylpropane-1,3-diamine and the like can be mentioned. N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine is preferable from the viewpoint of the effect of suppressing water droplet residue.

The component (B) may be used alone or in combination of two or more.
The content of the component (B) is preferably 0.0001 to 5% by mass, more preferably 0.01 to 1% by mass, and 0.01 to 0.% With respect to the total mass of the dishwasher detergent composition. 5% by mass is more preferable, and 0.01 to 0.1% by mass is particularly preferable.
When the content of the component (B) is not more than the above upper limit value, it is easy to suppress the generation of odor from the composition.
When the content of the component (B) is at least the above lower limit value, the effect of suppressing the residual water droplets is likely to be improved.

The mass ratio represented by the component (a1) / component (B) (hereinafter, also referred to as “a1 / B ratio”) is 0.1 to 500, preferably 5 to 100.
When the a1 / B ratio is within the above range, the effect of suppressing the residual water droplets is likely to be improved.

The total content of the component (A) and the component (B) (hereinafter, also referred to as “A + B”) is preferably 0.1 to 10.1% by mass with respect to the total mass of the dishwasher detergent composition. 0.5 to 5% by mass is more preferable, and 0.5 to 3% by mass is further preferable.
When A + B is within the above range, the effect of suppressing the remaining water droplets is enhanced.

<Arbitrary ingredient>
The dishwasher detergent composition of the present invention may contain any component normally contained in a detergent for washing dishes, as long as it does not contradict the object of the present invention. For example, a chelating agent having a molecular weight of 800 or less (hereinafter, also referred to as “(C) component”), an acrylic acid-based water-soluble polymer (hereinafter, also referred to as “(D) component”), an acidic thickening polysaccharide, a solvent, and a hydro. Contains ingredients such as polysaccharides, dispersants, thickeners, viscosity modifiers, enzymes, fragrances, colorants, preservatives, disinfectants, bleaching agents, bleaching activators, defoaming agents (silicone compounds, etc.) be able to.

The component (C) is a chelating agent having a molecular weight of 800 or less.
The component (C) is not particularly limited, and the general component (C) used so far in cleaning agents for dishwashers includes, for example, ethylenediamine tetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, and ethylenediamine disuccinic acid. , L-aspartic acid-N, N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediamine triacetic acid, glycol etherdiamine tetraacetic acid, L-glutamate diacetic acid, 1,3- Diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentacetic acid, triethylenetetraminehexacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2'-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethan Examples thereof include diphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphate, or salts thereof. As the salt constituting the component (C), an alkali metal salt is preferable, and a sodium salt and a potassium salt are more preferable.
Among them, the component (C) tends to increase the sterilizing power, so ethylenediamine tetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N, N-diacetic acid, and dihydroxy. Ethylethylene diamine diacetic acid, hydroxyethylimino diacetic acid, citric acid, hydroxyethyl ethylenediamine triacetic acid, glycol ether diamine tetraacetic acid, L-glutamate diacetic acid, 1,3-diamino-2-hydroxypropane tetraacetic acid, diethylenetriaminepentaacetic acid, tri One or more chelating agents selected from the group consisting of ethylenetetramine hexaacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2'-iminodysuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, and salts thereof. Is preferably used.
Further, citric acid, L-glutamate diacetic acid, methylglycine diacetic acid, diethylenetriaminepentacetic acid, ethylenediaminetetraacetic acid or salts thereof are preferable, and citric acid, ethylenediaminetetraacetic acid or salts thereof are particularly preferable.

The component (C) may be used alone or in combination of two or more.
When the dishwasher detergent composition of the present invention contains the component (C), the content of the component (C) is 3 to 25% by mass as an acid type with respect to the total mass of the dishwasher detergent composition. It is preferable, 8 to 18% by mass is more preferable, and 12 to 18% by mass is further preferable.
When the content of the component (C) is within the above range, the effect of suppressing the residual water droplets is likely to be improved.

The component (D) is an acrylic acid-based water-soluble polymer.
The component (D) contains a structural unit derived from (meth) acrylic acid or a derivative thereof. The component (D) may be a homopolymer or a copolymer.
Examples of the homopolymer include poly (meth) acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyitaconic acid or a salt thereof, and the like.
Examples of the copolymer include (meth) acrylic acid / maleic acid copolymer or a salt thereof, acrylic acid / crotonic acid copolymer or a salt thereof.
Of these, acrylic acid / maleic acid copolymers are particularly preferable, and the copolymerization ratio (molar ratio) is preferably 75/25 to 50/50. The acrylic acid / maleic acid copolymer preferably has a weight average molecular weight of 10,000 to 100,000 as measured by gel permeation chromatography, and more preferably 30,000 to 80,000. Moreover, a sodium salt, a potassium salt and the like are mentioned as a salt. Of these, sodium salts are preferable.

The component (D) may be used alone or in combination of two or more.
When the dishwasher detergent composition of the present invention contains the component (D), the content of the component (D) is 0.5 to 20% by mass with respect to the total mass of the dishwasher detergent composition. It is preferable, 1 to 12% by mass is more preferable, and 1 to 5% by mass is further preferable.
When the content of the component (D) is within the above range, the effect of suppressing the residual water droplets is likely to be improved.

Examples of the acidic thickening polysaccharide include polysaccharides to which monosaccharide oxides such as glucuronic acid, which is an oxide of glucose, galacturonic acid, which is an oxide of galactose, and mannuronic acid, which is an oxide of mannose, are bound. By containing the acidic thickening polysaccharide, it becomes easy to increase the viscosity of the composition.
Examples of the acidic thickening polysaccharide include xanthan gum, gellan gum, carrageenan, pectin, soybean polysaccharide, alginic acid, Arabic gum, Karaya gum, tragant gum, hyaluronic acid and the like.
Among them, xanthan gum, gellan gum and carrageenan are preferable, and xanthan gum and gellan gum are more preferable.
When the dishwasher cleaning composition of the present invention contains an acidic thickening polysaccharide, the content of the acidic thickening polysaccharide is 0.05 to 1. 5% by mass is preferable, 0.1 to 1% by mass is more preferable, and 0.2 to 1% by mass is further preferable.

The pH of the dishwasher detergent composition of the present invention at 25 ° C. is preferably 5 or more from the viewpoint of corrosiveness to the dishwasher. Further, from the viewpoint of low foaming property, 11 or less is preferable. More preferably, it is 6 to 10.
In the present invention, the pH of the dishwasher detergent composition indicates a value measured by adjusting the dishwasher detergent composition to 25 ° C. and using a pH meter or the like.

≪Manufacturing method of detergent composition for dishwasher≫
The detergent composition for a dishwasher of the present invention is not particularly limited, and a conventionally known production method can be used.
As a method for producing a liquid dishwasher detergent composition, it is prepared by mixing the component (A), the component (B), and if necessary, an arbitrary component.

≪How to use the detergent composition for dishwasher≫
The detergent composition for a dishwasher of the present invention may be used according to the model of the dishwasher and the degree of stain on the dishes and the like.
Examples of the method of washing the object to be washed by the dishwasher using the dishwasher detergent composition include a method having both washing and rinsing steps.
As a cleaning method, for example, a cleaning solution prepared by introducing tap water at room temperature (preferably about 5 to 30 ° C.) into a dishwasher is raised to a predetermined cleaning temperature (the temperature of the cleaning solution circulated during cleaning). A process of cleaning the object to be cleaned while warming (hereinafter referred to as "cleaning process"), a process of rinsing the object to be cleaned with tap water at room temperature (hereinafter referred to as "rinsing (1) process"), and a process of rinsing the object to be cleaned with tap water. While raising the temperature of tap water at room temperature from 70 to 75 ° C at 2 to 3 ° C / min, the cleaning object after the rinse (1) step is further rinsed (hereinafter referred to as “rinse (2) step”). ) Is mentioned. The cleaning time in the cleaning step is preferably 10 to 40 minutes.
In the case of a general standard course, the cleaning temperature in the cleaning step is about 55 to 65 ° C., and the heating rate is about 2 to 3 ° C./min. The low temperature course has, for example, a cleaning temperature of about 35 to 45 ° C. and a heating rate of about 1 ° C./min. The detergent composition for a dishwasher of the present invention is excellent in detergency against oil stains even in low temperature washing, and exhibits excellent detergency even when the washing temperature is, for example, 35 ° C.
In any course, the amount of the cleaning agent used at one time is preferably 2 to 9 g per about 3 liters of tap water in the case of a liquid cleaning agent.
Specifically, the dishwasher detergent composition of the present invention is added to water to prepare a cleaning solution containing 2 to 200% by mass of the component (A) and 0.02 to 20% by mass of the component (B). It is preferable to raise the temperature to 50 to 60 ° C. to wash the object to be washed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The unit of the blending amount in the table is "mass%", and each component indicates the pure content equivalent amount.
Blanks in the table indicate that the ingredient is not blended.
"Balance" means that water is blended so that the total blending amount (% by mass) of all the blending components contained in the composition of each example is 100% by mass. The content of the component (C) is the content as an anhydrous acid type.
The components shown in the table will be described below.

<Ingredient (A)>
-A1-1: Secondary sodium alkane sulfonate (secondary sodium alkane sulfonate having 14 to 17 carbon atoms, manufactured by Clarant Japan, trade name "HOSTAPUR SAS 30A").
-A1-2: Polyoxyethylene (average 3 mol) sodium lauryl ether sulfate (manufactured by Lion Specialty Chemicals, trade name: "Sannol LMT-1430").
-A1-3: Di (2-ethylhexyl) sodium sulfosuccinate (manufactured by Lion Specialty Chemicals, trade name "Repearl 870P").

-A2-1: Polyoxyalkylene alkyl ether, in formula (a2-1), R ²¹ is an alkyl group having 12 to 13 carbon atoms, X is -O-, s is 3, t is 3, and R ²² is a hydrogen atom. Compound, manufactured by Lion, trade name "NNAEP-3030").
-A2-2: Secondary alcohol ethoxylate, in formula (a2-1), R ²¹ is an alkyl group having 12 to 14 carbon atoms, X is -O-, s is 3.3, t is 0, and R ²² is. A compound of hydrogen atom, manufactured by Nippon Catalyst Co., Ltd., trade name "Sophthalol 33".
-A2-3: Alkyl polyglycoside, in formula (a2-2), R ²⁵ is a linear alkyl group having 6 carbon atoms, x is 0, G is a residue derived from glucose, and y is 1.3. , Made by Akzo Nobel, trade name "AG-6206".
-A2-4: Polyoxyethylene (40 mol on average) hardened castor oil, trade name "HC40", manufactured by Nippon Emulsion Co., Ltd.

-A3-1: n-dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals, trade name "Cadenax DM12D-W (C)".
-A3-2: Betaine lauryldimethylaminoacetic acid, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Amigen S".
-A3-3: Didecyldimethylammonium chloride manufactured by Lonza, trade name "Bardac2280G".
-A3-4: C18 dimethylaminopropylamide, manufactured by Toho Kagaku Co., Ltd., trade name "catinal MPAS") In formula (a3-5), a molecule (C16) in which ^R7 is a linear alkyl group having 15 carbon atoms. A mixture of R ⁷ = a molecule (C18) which is a linear alkyl group having 17 carbon atoms and C16: C18 = 3: 7 in mass ratio. A compound in which R ⁸ is a hydrogen atom, R ⁹ is a propylene group ((CH ₂ ) ₃ ), R ¹⁰ is a methyl group, and R ¹¹ is a methyl group.

<Ingredient (B)>
B-1: (N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine) (manufactured by Ronza, trade name "Lonzabac12.100", in formula (b-1), R ¹ is A compound which is an alkyl group having 12 carbon atoms and n is 3.

<Ingredient (C)>
-C-1: Citric acid, manufactured by Fuso Chemical Industry Co., Ltd., trade name "purified citric acid (anhydrous)".
-C-2: Methylglycine diacetic acid, manufactured by BASF, trade name "Toriron M".
-C-3: L-glutamic acid diacetate, manufactured by AkzoNobel, trade name "GL-47-S".

<(D) component>
-D-1: Carboxyvinyl polymer, manufactured by Sumitomo Seika, trade name "Akpek HV-505E.
-D-2: Acrylic acid / maleic acid copolymer soda salt, manufactured by Nippon Shokubai Co., Ltd., trade name "Aqualic TL-400".

<Other optional ingredients>
-Xanthan gum: Product name "KELZANT", manufactured by Sanshosha.
-Sodium cumene sulfonate: Product name "Tayca Tox N5040", manufactured by TAYCA.
-Amylase: Product name "Termamil Ultra 300L", manufactured by Novozymes.
-Protease: Product name "Sabinase Ultra 16XL", manufactured by Novozymes.
-PH adjuster: sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), sodium hydroxide: 48% sodium hydroxide (manufactured by Asahi Glass Co., Ltd.), granular sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), potassium hydroxide: 48% water Potassium oxide (manufactured by Asahi Glass Co., Ltd.), granular potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.).

<Preparation of detergent composition for dishwasher>
According to the compositions of Tables 1 to 5, 0.8 kg of the dishwasher detergent composition of each example was prepared by dissolving the component (A), the component (B), and the optional component in water as a solvent. ..
Specifically, xanthan gum and water were put into a 1 L beaker (diameter 12 cm) so as to be 50% by mass of the whole composition. The stirrer of HEIDON FBL1200 Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.) is equipped with a 4-blade paddle with a diameter of 7.5 cm, a width of 1.5 cm, and an angle of 45 degrees. The mixture was stirred at ~ 900 rpm. Then, after mixing the component (A), the component (B) and the component (C), sodium cumenesulfonate and a pH adjuster (sodium hydroxide or sulfuric acid) were added to obtain a mixed solution. The pH of the dishwasher detergent composition of each example was adjusted to pH 7.0 with a pH adjuster so as to have the pH value shown in the table. After adjusting to pH 7.0, enzymes (amylase, protease) are added, the remaining water is added so that the total composition becomes 100% by mass, and the dishwasher is stirred at the rotation speed of the stirrer at 650 rpm for 1 minute. A cleaning agent composition for use was obtained.
The remaining water was added so that the total content of the composition was 100% by mass, and the mixture was stirred at the rotation speed of the stirrer at 650 rpm for 1 minute to obtain a dishwasher detergent composition.
The pH (25 ° C.) of the composition was measured using a dishwasher detergent composition adjusted to 25 ° C. using a glass electrode type pH meter (HM-30G, manufactured by DKK-TOA CORPORATION). The measuring method was carried out in accordance with JIS Z 8802: 1984 "pH measuring method".

<Evaluation of detergent for dishwasher>
The compositions of each Example and Comparative Example were evaluated by the evaluation methods shown below, and the results are also shown in the table.
As a dishwasher, an automatic dishwasher (manufactured by Panasonic Corporation, model NP-40SX2) was used. In each evaluation, the washing process was performed by operating in the standard course (power saving mode or normal mode) set in the automatic dishwasher. In the power saving mode, the water temperature in the washing step is set to be 15 ° C. lower than that in the normal mode. The contents of the standard course (power saving mode) are shown below.
・ Standard course (power saving mode):
After putting 2 to 9 g of the composition (for 3 L of tap water) into the automatic dishwasher, the washing liquid prepared by introducing tap water at about 5 ° C into the refrigerator is charged at 2 to 3 ° C / min up to 40 ° C. Wash for 20 minutes while raising the temperature with, and drain the washing liquid. Then, fresh tap water is introduced, and rinsing (2 minutes / time) and drainage are repeated 3 times. After draining, introduce new tap water, rinse once (final rinse) for 20 minutes while raising the temperature to 70 ° C at 2-3 ° C / min, and after draining, dry the dishes while circulating warm air. do.
-The standard course (normal mode) is the standard course (power saving mode), and the other operations of washing for 20 minutes while raising the cleaning liquid to 55 ° C at 2 to 3 ° C / min are the standard course (power saving mode). ).

<Evaluation of drainage>
Five glass glasses (diameter about 6 cm, height 10 cm) containing 1 g of fresh cream are installed in the dishwasher, and after adding the detergent composition for the dishwasher, the automatic dishwasher is used with water at 5 ° C. I drove on the standard course. The absence of water droplets (white spots) after drying was evaluated according to the following sensory evaluation criteria, and the total value of 5 glasses was calculated. A score of D or higher was accepted. White spots of 1 to 100 mm ² were counted as one water droplet trace. When a plurality of water droplet traces overlapped, they were counted as one water droplet trace.
(Evaluation criteria)
A: The number of water droplets is 0-5.
B: The number of water droplets is 6 to 10.
C: The number of water droplets is 11 to 15.
D: The number of water droplets is 16 to 25.
E: The number of water droplets is 26 to 35.
F: The number of water droplets is 36 to 45.
G: The number of water droplets is 46 or more.

Examples 1 to 26 to which the present invention was applied were excellent in the effect of suppressing the residual water droplets.
Comparative Example 1 having an a1 / B ratio of less than 0.1 was inferior in the effect of suppressing the residual water droplets.
Comparative Example 2 having an a1 / B ratio of more than 500 was inferior in the effect of suppressing the residual water droplets.

Claims (7)

Includes component (A) and component (B)
The component (A) is a surfactant, and the component (A) is a surfactant.
The component (B) is a compound represented by the following formula (b-1).
The component (A) contains a non-soap-based anionic surfactant (a1) having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms .
A dishwasher detergent composition having a mass ratio of the component (a1) / the component (B) of 0.1 to 500.
R ¹ -N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
(In the formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group of a branched chain of the number 8-18; n is an integer of 2-6.) The detergent composition for a dishwasher according to claim 1 , wherein the content of the component (a1) is 40% by mass or more with respect to the total mass of the component (A). The dishwasher detergent composition according to claim 1 or 2 , wherein the component (A) contains a nonionic surfactant (a2). The invention according to any one of claims 1 to 3, wherein the component (a1) comprises at least one selected from the group consisting of an alkane sulfonate, a dialkyl sulfosuccinate, and a polyoxyalkylene alkyl ether sulfate ester salt. Detergent composition for dishwashers. Further contains a chelating agent (C),
The detergent composition for a dishwasher according to any one of claims 1 to 4 , wherein the chelating agent has a molecular weight of 800 or less. The detergent composition for a dishwasher according to any one of claims 1 to 5, further comprising an acrylic acid-based water-soluble polymer (D). Further, it contains a chelating agent (C) and an acrylic acid-based water-soluble polymer (D).
The content of the component (A) is 0.1 to 10% by mass with respect to the total mass of the detergent composition.
The content of the component (B) is 0.0001 to 5% by mass with respect to the total mass of the detergent composition.
The content of the component (C) is 3 to 25% by mass with respect to the total mass of the detergent composition.
The content of the component (D) is 0.5 to 20% by mass with respect to the total mass of the detergent composition.
The detergent composition for a dishwasher according to any one of claims 1 to 4.